Grain size distribution and clay mineralogy of upper Miocene sediments of ODP Hole 107-652A

The upper Miocene sedimentary sequence of Site 652, located on the lower continental margin of eastern Sardinia, was cored and logged during Ocean Drilling Program (ODP) Leg 107. Geophysical and geochemical logs from the interval 170-365 m below seafloor (mbsf), as well as various core measurements (CaCO3, grain size, X-ray diffraction), provide a mineralogical-geochemical picture that is interpreted in the framework of the climatic and tectonic evolution of the western Tyrrhenian. The results indicate the presence of short- and long-term mineralogical variations. Short-term variations are represented by calcium-carbonate fluctuations in which the amount of CaCO3 is correlated to the grain size of the sediments; coarser sediments are associated with high carbonate content and abundant detrital material. Long-term variation corresponds to a gross grain-size change in the upper part of the sequence, where predominantly fine-grained sediments may indicate a gradual deepening of the lacustrine basin towards the Pliocene. Regional climatic changes and rift-related tectonism are possible causes of this variability in the sedimentation patterns. The clay association is characterized by chlorite, illite, and smectite as dominant minerals, as well as mixed-layers clays, kaolinite, and palygorskite. Chlorite, mixed-layers clays, and illite increase at the expense of smectite below the pebble zone (335 mbsf). This is indicative of diagenetic processes related to the high geothermal gradient and to the chemistry of the evaporative pore waters, rather than to changes in the depositional environment.

Chemical and isotopical analsyes of DSDP Hole 34-321 basalts

A blue-green smectite (iron-rich saponite) and green mica (celadonite) are the dominant sheet silicates in veins within the 10.5 m of basalt cored during DSDP Leg 34, Site 32l, in the Nazca plate. Oxygen isotopic analyses of these clays, and associated calcite, indicate a formation temperature of <25°C. Celadonite contains appreciable Fe2O3, K2O and SiO2, intermediate MgO, and very little Al2O3. Celadonite is commonly associated with goethite and hematite, which suggests that this phase formed by precipitation within a dominantly oxygenated environment of components leached from basalt and provided by seawater. A mass balance estimate indicates that celadonite formation can remove no more than 15% of the K annually transported to the oceans by rivers. In contrast, iron-rich saponite containing significant Al2O3 appears to have precipitated from a nonoxidizing, distinctly alkaline fluid containing a high Na/K ratio relative to unmodified seawater. Seawater-basalt interaction at low temperatures, resulting in the formation of celadonite and smectite may explain chemical gradients observed in interstitial waters of sediments overlying basalts.

Magnetic remanence acquisition in DSDP Leg 73 Holes

The major magnetic mineral in the turbidites and slumped sediments recovered at Leg 73 drill sites was near to magnetite in composition and in the form of small multidomain particles. There was no variation in magnetic mineralogy with the lithology. The variations in the intensities and directions of the natural remanent magnetization could be explained in terms of postdepositional grain rotations within the wet sediment. In the sands realignment was partial, whereas in some of the slumps the entire remanent magnetization was reset. Fine-particle magnetite was also the main magnetic constituent of the red clays. A significant proportion of a higher-coercivity mineral was also present. The magnetic characteristics of the red clays are explained as a combination of concentration and grain rotation effects. The implications to the assessment of the reliability of paleomagnetic data are discussed. Note: Conversion factors are as follows: 1 Am**2/kg = 1 emu/g, and 80 A/m about 1 Oe.

Geochemistry of ODP Leg 127 igneous rocks

Legs 127 and 128 of the Ocean Drilling Program cored basement samples from two sites in the Yamato Basin (Sites 794 and 797) and one site in the Japan Basin (Site 795) of the Japan Sea. These samples represent sills and lava flows erupted or shallowly intruded in a marine environment during backarc extension and spreading in the middle Miocene. In this paper, we describe the geochemical characteristics of these igneous units using 52 new instrumental neutron activation analyses (INAA), 8 new X-ray fluorescence (XRF) analyses, and previous shipboard XRF analyses. The sills intruded into soft sediment at Sites 794 and 797 were subject to extensive hydrothermal activity, estimated at <230° C under subgreenschist facies conditions, which heavily to totally altered the fine-grained unit margins and moderately to heavily altered the coarse-grained unit interiors. Diagenesis further altered the composition of these igneous bodies and lava flows at Sites 794, 795, and 797, most intensely at unit margins. Our study of two well-sampled units shows that Mg, Ca, Sr, and the large-ion lithophile elements (LILE) mobilized during alteration, and that the concentrations of Y, Yb, and Lu decreased and Ce increased in the most severely altered samples. Nevertheless, our study shows that the rare-earth elements (REE) were relatively immobile in the majority of the samples, even where secondary mixed-layer clays comprised the great majority of the rock. Fresher Yamato Basin samples are compositionally heterogenous tholeiitic basalts and dolerites. At Site 794 in the north-central portion of the basin, Units 1 to 5 (upper basement) comprise mildly light rare-earth element (LREE) enriched basalts and dolerites (chondrite-normalized La/Sm of 1.4-1.8), while the stratigraphically lower Units 6 to 9 are less enriched dolerites with (La/Sm)N of 0.7-1.3. All Site 794 samples lack Nb and Ta depletions and LILE enrichments, lacking a strong subduction-related incompatible element geochemical signature. At Site 797 in the western margin of the basin, two stratigraphically-definable unit groups also occur. The upper nine units are incompatible-element depleted tholeiitic sills and flows with strong depletions of Nb and Ta relative to normal mid-ocean ridge basalt (N-MORB). The lower twelve sills represent LREE-enriched tholeiites (normalized La/Sm ranges from 1.1 to 1.8), with distinctly higher LILE and high field-strength element (HFSE) contents. At Site 795 at the northern margin of the Japan Sea, three eruptive units consist of basaltic andesite to calc-alkaline basalt (normalized La/Sm of 1.1 to 1.5) containing moderate depletions of the HFSE relative to N-MORB. The LILE-depleted nature of these samples precludes their origin in a continental arc, indicating that they more likely erupted within a rifting oceanic arc system. The heterogenous nature of the Japan Sea rocks indicate that they were derived at each site from multiple parental magmas generated from a compositionally heterogenous mantle source. Their chemistry is intermediate in character between arc basalts, MORB, and intraplate basalts, and implies little involvement of continental crust at any point in their genesis. Their flat chondrite-normalized, medium-to-heavy rare earth patterns indicate that the primary magmas which produced them last equilibrated with and segregated from spinel lherzolite at shallow depths (<30 kbar). In strong contrast to their isotopic compositional arrays, subduction-related geochemical signatures are usually poorly defined. No basin-wide temporal or geographic systematics of rock chemistry may be confidently detailed; instead, the data show both intimate (site-specific) and widespread backarc mantle heterogeneity over a narrow (2 Ma or so) range in time, with mantle heterogeneity most closely resembling a "plum-pudding" model.

Consolidation properties and hydraulic conductivities of sediments from ODP Leg 207 sites

The stress history, permeability, and compressibility of sediments from Demerara Rise recovered during Ocean Drilling Program Leg 207 were determined using one-dimensional incremental load consolidation and low-gradient flow pump permeability tests. Relationships among void ratio, effective stress, and hydraulic conductivity are presented for sampled lithologic units and used to reconstruct effective stress, permeability, and in situ void ratio profiles for a transect of three sites across Demerara Rise. Results confirm that a significant erosional event occurred on the northeastern flank of the rise during the late Miocene, resulting in the removal of ~220 m of upper Oligocene-Miocene deposits. Although Neogene and Paleogene sediments tend to be overconsolidated, Cretaceous sediments are normally consolidated to underconsolidated, suggesting the presence of overpressure. A pronounced drop in permeability occurs at the transition from the Cretaceous black shales into the overlying Maastrichtian-upper Paleocene chalks and clays. The development of a hydraulic seal at this boundary may be responsible for overpressure in the Cretaceous deposits, leading to the lower overconsolidation ratios of these sediments. Coupled with large regional variations in sediment thickness (overburden stresses), the higher permeability overpressured Cretaceous sediments represent a regional lateral fluid conduit on Demerara Rise, possibly venting methane-rich fluids where it outcrops on the margin's northeastern flank.

Clay mineralogy of Cape Roberts sediment cores

The clay mineral assemblages of the ca. 1600 m thick Cenozoic sedimentary succession recovered at the CRP-1, CRP-2/2A and CRP-3 drill sites off Cape Roberts on the McMurdo Sound shelf, Antarctica, were analysed in order to reconstruct the palaeoclimate and the glacial history of this part of Antarctica. The sequence can be subdivided into seven clay mineral units that reflect the transition from humid to subpolar and polar conditions. Unit I (35-33.6 Ma) is characterised by an almost monomineralic assemblage consisting of well crystalline, authigenic smectite, and therefore does not allow a palaeoclimatic reconstruction. Unit II (33.6-33.1 Ma) has also a monomineralic clay mineral composition. However, the assemblage consists of variably crystallized smectite that, at least in part, is of detrital origin and indicates chemical weathering under a humid climate. The main source area for the clays was in the Transantarctic Mountains. Minor amounts of illite and chlorite appear for the first time in Unit III (33.1-31 Ma) and suggest subordinate physical weathering. The sediments of Unit IV (31-30.5 Ma) have strongly variable smectite and illite concentrations indicating an alternation of chemical weathering periods and physical weathering periods. Unit V (30.5-24.2 Ma) shows a further shift towards physical weathering. Unit VI (24.2-18.5 Ma) indicates strong physical weathering under a cold climate with persistent and intense illite formation. Unit VII (18.5 Ma to present) documents an additional input of smectite derived from the McMurdo Volcanic Group in the south.

Stable chlorine isotopes in pore waters from DSDP Hole 79-546 and ODP Hole 131-808C

Stable Cl isotope ratios, measured in marine pore waters associated with the Barbados and Nankai subduction zones, extend significantly (to ~-8 per mil) the range of d37Cl values reported for natural waters. These relatively large negative values, together with geologic and chemical evidence from Barbados and Nankai and recent laboratory data showing that hydrous silicate minerals (i.e., those with structural OH sites) are enriched up to 7.5 per mil in 37Cl relative to seawater, strongly suggest that the isotopic composition of Cl in pore waters from subduction zones reflects diagenetic and metamorphic dehydration and transformation reactions. These reactions involve clays and/or other hydrous silicate phases at depth in the fluid source regions. Chlorine therefore cannot be considered geochemically conservative in these systems. The uptake of Cl by hydrous phases provides a mechanism by which Cl can be cycled into the mantle through subduction zones. Thus, stable Cl isotopes should help in determining the extent to which Cl and companion excess volatiles like H2O and CO2 cycle between the crust and mantle.

Post-glacial pollen record from Yorkshire

The stratigraphy and pollen analysis of the deposits show that this is a lake basin which during the Late-glacial period was partially filled by lake clays and muds. One of the main interests of the pollen diagrams lies in the division of zone i into three suh-zones showing a minor climatic oscillation which seems to be comparable with the Boiling oscillation of northern Europe. During Post-glacial time the greater part of the deposits has been muds but on one side a fen developed which in early zone VI was sufficiently dry to support birch and pine wood. Later in zone VI the water table must have risen slightly because the fen peats were gradually covered by a rather oxidized mud suggesting that the fen became replaced by a shallow swamp with a widely fluctuating water table. In the Atlantic period the basin was reflooded and the more central deposits were covered by a layer of mud. Later in the central region, swamp and eventually Sphagnum bog communities developed. The whole area is now covered by a sihy soil and forms a flat meadowland.

Glacial-interglacial record of ODP Site 181-1119 in the Canterbury Bright, Southwest Pacific Ocean

Ocean Drilling Program (ODP) Site 1119 is located at water depth 395 m near the subtropical front (STF; here represented by the Southland Front), just downslope from the shelf edge of eastern South Island, New Zealand. The upper 86.19 metres composite depth (mcd) of Site 1119 sediment was deposited at an average sedimentation rate of 34 cm/kyr during Marine Isotope Stages (MIS) 1-8 (0-252 ka), and is underlain across a ~25 kyr intra-MIS 8 unconformity by MIS 8.5-11 (277-367 ka) and older sediment deposited at ~14 cm/kyr. A time scale is assigned to Site 1119 using radiocarbon dates for the period back to ~39 ka, and, prior to then, by matching its climatic record with that of the Vostok ice core, which it closely resembles. Four palaeoceanographic proxy measures for surface water masses vary together with the sandy-muddy, glacial-interglacial (G/I) cyclicity at the site. Interglacial intervals are characterised by heavy delta13C, high colour reflectance (a proxy for carbonate content), low Q-ray (a proxy for clay content) and light delta18O; conversely, glacial intervals exhibit light delta13C, low reflectance, high Q-ray and heavy delta18O signatures. Early interglacial intervals are represented by silty clays with 10-105-cm-thick beds of sharp-based (Chondrites-burrowed), shelly, graded, fine sand. The sands are rich in foraminifera, and were deposited distant from the shoreline under the influence of longitudinal flow in relatively deep water. Glacial intervals comprise mostly micaceous silty clay, though with some thin (2-10 cm thick) sands present also at peak cold periods, and contain the cold-water scallop Zygochlamys delicatula. Interglacial sandy intervals are characterised by relatively low sedimentation rates of 5-32 cm/kyr; cold climate intervals MIS 10, 6 and 2 have successively higher sedimentation rates of 45, 69 and 140 cm/kyr. Counter-intuitively,and forced by the bathymetric control of a laterally-moving shoreline during G/I and I/G transitions, the 1119 core records a southeasterly (seaward) movement of the STF during early glacial periods, accompanied by the incursion of subtropical water (STW) above the site, and northwesterly (landward) movement during late glacial and interglacial times, resulting in a dominant influence then of subantarctic surface water (SAW). The history of passage of these different water masses at the site is clearly delineated by their characteristic delta13C values. The intervals of thin, graded sands-muds which occur within MIS 2-3, 6, 7.4 and 10 indicate the onset at times of peak cold of intermittent bottom currents caused by strengthened and expanded frontal flows along the STF, which at such times lay near Site 1119 in close proximity to seaward-encroaching subantarctic waters within the Bounty gyre. In common with other nearby Southern Hemisphere records, the cold period which represents the last glacial maximum lasted between ~23-18 ka at Site 1119, during which time the STF and Subantarctic Front (SAF) probably merged into a single intense frontal zone around the head of the adjacent Bounty Trough.

Chemical composition of interstitial solutions from sediments of DSDP Legs 6-8, 11, 12, 14, 15, and 22

Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments. Pelagic clays and slowly deposited (<1 cm/1000 yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters. In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/1000 yr the changes chiefly involve gains of Ca(2+) and Sr(2+) and losses of Mg(2+) which balance the Ca(2+) enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr(2+) may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg(2+) for Ca(2+) during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca(2+) and Sr(2+) enrichment is again characteristic, but Mg(2+) losses exceed Ca(2+) gains with the excess being balanced by SO4(post staggered 2-) losses. The data indicate that the reactions are similar to those noted above, except that the Ca(2+) released is not kept in solution but is precipitated by the HCO3(post staggered -) produced in SO4(post staggered 2-) reduction. In both these types of pore waters Na(+) is usually conservative, but K(+) depletions are frequent. In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na(+), Si and CO2, and slight enhancement in Cl(-). The changes are attributed to exchange of Na(+) for Ca(2+) in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity. Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO4(post staggered 2-), strong HCO3(post staggered -) enrichment, formation of NH4(post staggered +), and methane synthesis from H2 and CO2 once SO4(post staggered 2-) is eliminated. K+ and often Na+ (slightly) are depleted in the interstitial waters. Ca(2+) depletion may occur owing to precipitation of CaCO3. In most cases interstitial Cl- remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl- are observed in some sediments adjacent to continents.

Geochemistry of subducted volcaniclastic sediments from Mariana arc magmas

The phase relations of natural volcaniclastic sediments from the west Pacific Ocean were investigated experimentally at conditions of 3-6 GPa and 800-900 °C with 10 wt.% added H2O (in addition to ~ 10 wt.% structurally-bound H2O) to induce hydrous melting. Volcaniclastic sediments are shown to produce a sub-solidus assemblage of garnet, clinopyroxene, biotite, quartz/coesite and the accessory phases rutile ± Fe-Ti oxide ± apatite ± monazite ± zircon. Hydrous melt appears at temperatures exceeding 800-850 °C, irrespective of pressure. The melt-producing reaction consumes clinopyroxene, biotite and quartz/coesite and produces orthopyroxene. These phase relations differ from those of pelagic clays and K-bearing mid ocean ridge basalts (e.g. altered oceanic crust) that contain phengite, rather than biotite, as a sub-solidus phase. Despite their relatively high melt productivity, the wet solidus for volcaniclastic sediments is found to be higher (825-850 °C) than other marine sediments (700-750 °C) at 3 GPa. This trend is reversed at high-pressure conditions (6 GPa) where the biotite melting reaction occurs at lower temperatures (800-850 °C) than the phengite melting reaction (900-1000 °C). Trace element data was obtained from the 3 GPa run products, showing that partial melts are depleted in heavy rare earth elements (REE) and high field strength elements (HFSE), due to the presence of residual garnet and rutile, and are enriched in large ion lithophile elements (LILE), except for Sr and Ba. This is in contrast to previous experimental studies on pelagic sediments at sub-arc depths, where Sr and Ba are among the most enriched trace elements in glasses. This behavior can be partly attributed to the presence of residual apatite, which also host some light REE in our supra-solidus residues. Our new experimental results account for a wide range of trace element and U-series geochemical features of the sedimentary component of the Mariana arc magmas, including imparting a substantial Nb anomaly to melts from an anomaly-free protolith.

(Table 3) Contents of phosphorus, iron, and manganese in various zones of Fe-Mn nodules from the Pacific radiolarian belt

Phosphorus content in the surface layer of bottom sediments varies from 0.07% to 0.73%. Clayey radiolarian and radiolarian clayey oozes contain 0.12% P, miopelagic clays 0.21% P, and sediments with high iron and manganese concentrations 0.46% P (average contents). Phosphorus content of iron-manganese nodules varies from 0.14% to 0.39%, average 0.19%. Correlation between phosphorus contents in nodules and surrounding sediments is indicated indirectly by P/Fe ratio. Phosphorus is non-uniformly distributed in some nodules and sometimes correlates with iron. Accumulation of phosphorus in iron-manganese nodules is governed by a degree of manganese predominance in ore components.